Maya Moore was the top vote-getter, but told the league she was unable to perform the captain duties.
"I'm once again blown away at the support I've received through votes by our amazing basketball fans. I'm so grateful for all the love," Moore said. "As somebody who is receiving a lot of attention, I wanted to take an opportunity to broaden that focus. I'm thrilled for everyone selected and now more than ever I'm looking forward to just being a fellow fan of all the greatness I'm surrounded by in this league."
With Moore passing on the opportunity to be captain, that gave Parker the nod as she finished third in the voting by fans, players, coaches and the media.
"I'm honored to be named captain and am excited to be joined by two of my teammates," Parker said. "It should be fun and it's good to see the league mixing it up with the captain format."
Parker and Delle Donne will draft players from the 20 other All-Stars who were announced Tuesday.
"I'm glad that Maya turned down her role so that I can have the first pick," Delle Donne said laughing in a phone interview with the AP. "I've got everyone's name written down and their position. You can't pick wrong as you have really great players out there."
Delle Donne wouldn't say who she's picking first, but did say that she feels loyalty to Mystics teammate Kristi Toliver to draft her.
"The one pick I will give away is that she will be on my team," she said.
Parker has two Sparks teammates in the pool with Nneka Ogwumike and Chelsea Gray.
Other players that Delle Donne and Parker can choose from include Sue Bird, who made a record 11th All-Star Game, breaking a tie with Tamika Catchings for most all-time.
"Seventeen years ago, if you told me I'd be setting a new record with 11 All-Star appearances, I would have called you crazy," Bird said. "It's a testament to my teammates and coaches throughout the years, and an absolute honor given all of the greats who have played in this league."
Rookie A'ja Wilson will play in her first All-Star contest, as well as Jewell Loyd. Dallas Wings center Liz Cambage will play in her second one. Earlier on Tuesday, she broke the WNBA single-game scoring record when she had 53 points against New York.
"That was incredible, it bumped her up the list for sure," Delle Donne said.
The WNBA took conference affiliation out of the midseason game and 16 of the 22 All-Stars were from the Western Conference. That group includes Diana Taurasi, Sylvia Fowles and Seimone Augustus. Fowles, Moore and Augustus will get a chance to play in front of their home fans; the All-Star Game is in Minnesota on July 28.
"It's going to be great," Phoenix coach Sandy Brondello said. "There's so much talent out there, it's like coaching a USA Basketball team. It's going to be nice to coach some players that normally I don't get the chance to."
Brondello, who will coach Australia in the women's basketball world cup in September, will be teamed with Parker.
Delle Donne's team will be led by Seattle coach Dan Hughes, who has guided the Storm to the league's best record.
The captains will draft their teams on Wednesday. The teams will be revealed Thursday night. The draft won't be televised, which Delle Donne wasn't completely upset about.
"I'd like to get one year under my belt," she said. "Wouldn't want to be put on blast with selections."
Fans accounted for 40 percent of the vote, while current players, current head coaches and a media panel accounted for 20 percent each. Players were not allowed to vote for their teammates. Coaches could not vote for players on their own team.
Moore was the leading vote-getter among fans (47,620). She was followed by Delle Donne (42,171), Parker (38,575), Bird (37,098) and Taurasi (35,687). Fans cast 44 percent more votes than they did last year (873,437 vs. 604,680).
Wilson was the only rookie to make the All-Star list and every team has at least one player in the game except for last-place Indiana.
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